DE2445674A1 - MIXTURE AND ITS USE AS A FLAVORING AGENT - Google Patents

Description

In the past a lot of attention has been paid to the Reproduction aimed at taste notes that usually define the bitter character of certain foods * In the In fact, there is a need for flavor industry flavoring ingredients or compositions of the same to improve the aroma of beverages or solid foods, especially those that imitate cocoa or a cocoa Substitutes include by giving these products the particular bitterness that characterizes natural calcium products. So far, however, no satisfactory solution has been found for this problem.

The term used here - "bitterness" is intended to describe the taste properties of a given substance in order to develop a substance define bitter taste.

5098 15/1328

Most of these substances come from the plant kingdom and are often found in many different plants, such as those, belonging to the Gentianaceae, 'iTf-.rnpositae and Mint families belong. Also some foods based on here.i see primeval. sprungs have a bitter taste after they have been determined Treatments have been subjected.

The so-called "bitter substances", however, do not include any alkaloid derivatives of purine, whose bitter taste is often a side effect is viewed (K. Herrmann, Deutsche Lebensmittelr-indschau, 68, 105 (1972)).

Most of the bitter substances known to date belong either to the class of terpenoids with a lactonic or prketonic functional group or to that of the phenol derivatives, such as, for example, the compounds of the Fiavanone series in citrus fruits. It is also known as ° eptide with a bitter taste, and its organoleptic properties have been described in various scientific publications (vpI. Zeit, für Lebensmitteluntersuch. Frrsch., 147 , 64 (1971); idem, 149, 321 (W2): Agr.Biol. Chem., ~ 5 ±, 729 (197O); J. Food Sci., 3> 5, 215 (1 97O)).

Certain amino acids (see e.g. Greenstein and Winitz, • Chemistry of the Aminoacids ", Vol. I, 0. Wiley (1961), p 150) and certain oligopeptides ("Annual Meeting of the Agr. Chem. Soc. Japan, 42 (1972)) develop bitter taste notes.

In the course of the last few years there are different theories has been established to better 'define the relationships that exist between the chemical structure of a given substance

509815/1328 BAD ORiGfNAL

and the developed bitterness (cf. "Nature", 223: 97-9 (1969)). However, it is expressly pointed out that that with the current state of knowledge it is impossible the organoleptic properties of a compound. the only basis to predict their chemical structure. Therefore it is not unexpected that the discovery of new flavoring ingredients, especially bitter flavoring ingredients, is often left to chance.

The present invention provides an Arocgpr ^ ready that as active ingredients comprises compounds A and B, wherein dit Compound A to the group of an amino acid and a djigopeptide or a mixture of oligopeptides, while the Compound B is a purine derivative of the formula:

1 2
is in which R and R are each a methyl radical or one of them is hydrogen and the other is a methyl radical. .

Surprisingly, it has now been found that it.by using this flavor preparation according to the invention is possible, the organoleptic Properties of food, pet food, beverages, "!, pharmaceutical preparations and tobacco products too modify, improve or strengthen. In particular, it has been found that by using the inventive

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Preparation is possible to impart a characteristic bitterness to the products to which it has been added verbesGsrn.

The present invention also relates to food and beverages that have a low but taste-modifying effect Amount of this preparation was added.

The present invention relates in particular to aromatization of cocoa, cocoa products or imitating cocoa Replacement and, in general, the improvement of organoleptic properties.

Another aspect of the present invention is a method to enhance, improve or modify the taste and mimicking the aromas of cocoa, cocoa products or cocoa Substitute substances, which is characterized by the fact that one can use them Aroma preparation adds the compounds as active ingredients A and B, wherein compound A belongs to the group of one Amino acid and an oligopeptide or a mixture of oligopeptides while the compound B is a purine derivative of the formula I.

According to the method of the invention, it is possible to do the usual correctly reproduce bitter and astringent taste sensations, which. in the human sensory system through the ingestion of foods containing cocoa will.

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- £ 2U5674

In the past, the cocoa flavor has been thoroughly researched and to reconstitute its natural flavor F .- 'nd various solutions proposed morden.

For example, US Patent 2,835,590 includes the manufacture, nines artificial chocolate flavor by a method of treatment of a saccharide with a Oligopepti <i, 2-u Aminosäureinheiten. Bitterness and astringency were given in this case by adding substances such as theohvomin, caffeine, quinine or naringin and tannins to the aroma preparation.

In the past, cocoa tasted the bigger Attributed to presence of TheobiOmin and Laffeine; it was 'In particular, it was assumed that its bitterness was dependent on the relative proportions of these purines ("Har.cinbuch der LebensmittelcheraiF" Vol. VI, Springer Verlag (1.97O), page 232; Deutsche Lebensmittelrundschau j58, 140 (1972)).

It has now been found that the presence of one or the other of these purines is a necessary but insufficient condition for reconstituting the cocoa flavor. The presence of an amino acid or an oligopeptide or a mixture of oligopeptides is also essential. Suitable oligopeptides include di-, tri-, tetra-, penta- and hexapeptides, but dipeptides are preferred. Of the various dipeptides that can be used according to the invention as aromatic trends in cobalt constituent B, the following open-ended and cyclic peptides are of particular interest:

Gly-Ala, Gly-Val, Gly-Leu, Giy.-Phe, Gly-Pro, Ala-Leu, Ala-Var, Ala-Phe, Ala-Pro, VaI-Leu, Val-Phe, Val-Pro,

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as-.,;

Leu-Phe,
Gly-Gly,
Leu-leu,

Leu-Pro,
Ala-Ala,
Phe-Phe,

Phe-Pro, VaI-Va1,

(Cyclo)
(Cycü;) ■
(Cyclo)
(Cyclo)

(Cyclo) - (Cyclo; ·
(Cyclo)
(Cyclo)
(Cyclo)
(Cyclo)
(Cyclo)
(Cyclo)

■ Gly-Ala- ■ Gly-Val- ■ Gly-Leu-Gly-Phe- • Gly-Prc- ■ Ala-Leu- ■ Ala-Val- ■ Ala-Phe- • Ala-Pro- • val-Leu- • Val-I'ne- • Val-Pro-

(Cyclo) -Lsu-Phe- (Cyc? O) -Leu-Pro- (Cyclo) -Phe-Pro- (Cyclo) -rro-Asn- (Cyclo) -Asn-Phe-

(Cyclo) -Gly-Gly-Ber.; 39, 752 (1906) Ar ".; 363, 336 (1908) At ·., "39, 2893 (I9O6) Ann., '363, 1 (1 ^ 08) Ann .; 363, 118 (19Od) Ber .. / 39, 2893 (1906) Ann .; 363, 136 (190B)

W. Schoeiler, Di & sertation Berlin (I906) Ber., · 37, 28 * 12 (190I) Ann., '36_3, 136 (1908)

Z. phys. Chem., 2ΐ £, 63 (1933) Hoppe-Seyler's. Z. physiol.Chora., ± 32, 1 (19 ^ ¹ I)

Coll. Czech. Chain. Comm. , 32.3780 (1967 Ann., 363, 118 (1908)

J. Biol. Formerly, 155, 535 (191 ".)

Hoppe-Seyler's Z. physiol. Chem., 17H, 76 (1928)

J. Pract. Chemistry, "26., 175 (I887)

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(CyCIo) -AIa-AIa- Anri./T3_4_, 372 (1865)

(CyClO) -VaI-VaI- Ann. /; 3_6_3, 136 (1908)

ACyCIo) -LeU-LeU- Ann. , "6JJ, 16 (1849)»

^: .. (Cyclo) -Phe-Phe- Ann./ 229, 1.79 (1883)

In the course of the present description, the cyclic dipeptides, which are also known as "diketopiperazines", are referred to by the customary abbreviation which the term "cyclo" is introduced. For example, "Ala-. ^P .la" means Al & r-yl-alanine, a compound of the formula

'CH-CH-C-NH-CH-COOH

dlβ is also defined as H-Ala-Ala-DH, while the designation "(CyCIo) -AIa-AIa-" refers to 2,5-dim> 3thyl-3,6-diketopiperazine, a compound of the following formula relates:

; H-.C-CH 3 I s

T J

Tl

In the above list of compounds it is ranked according to the chemical The name of the reference is given which carries out a process for their preparation. Some of the compounds mentioned are in the Commercially available, and one is new and indicated by the abbreviation n.c. Their production is that of the well-known Compounds can be made by a synthesis according to the following reaction scheme:

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R ³ O

base

E-NH-CH-C-OH + Cl-C-OC ₂ H ₅ -

R- ⁷ O 0 I II Ii - »Z-HH-CH-COC-OC ₀ H ₁

base

R- * O R O

H ₂ / Pd

Ii ₂ N-CH-C-NH-CH-C-CCH, f-

R ¹¹ O

+ H ₂ N-CH-C-OCH ₃ -HCl

.. R ³ O RO I II I II

Z-NH-CH-C-NH-CH-P-OCH + CO + C ₂ H OH

, ^ cIisation

-OH ₇ OH

0 II

³ -Cif ^X NH I (Ii

HN HC-R '

In the above scheme, Z denotes a carbobenzoxyl radical

Formula:

CH ₂ -OC-

3 4
in which R and R are the characteristic substituents in

Molecule of the special amino-

3

mean acid. For example, R and R can each be a hydrogen atom or an alkyl radical, tuie methyl, ethyl, ropyl, isopentyl, 2-methylbutyl or ^ -phenylethyl.

To illustrate the production of the dipeptides according to the invention, reference is made to the following method (cf. also HeIv.Chim. Acta, 2i> ⁸⁷⁴ (1951) and D.Org.Chem., 21t 364 (1968)).

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5 millimoles of the N-carbobenzoxylic derivative of the selected amino acid were dissolved in a solution of 7.5 millimoles of N-methylmorpholine in 20 ecm of anhydrous tetrahydrofuran. The solution thus obtained and / urde on etiua -1O ⁰ C. cooled, ': nd at' this temperature, 5.2 millimoles Äthy. ¹ chlorocarbonate added. Then the reaction mixture was stirred for 15 minutes.

A suspension of 5 Millimo] Methylesters of the selected for coupling amino acid hydrochloride and 7.5 mil] IMOL W-Mebhylmorpholin in 10 cc of dimethylformamide were added to this mixture, the temperature was increased slowly with stirring at about 20-25 ⁰ C.. Filtration and evaporation of the volatile components under vacuum (bath temperature about 60 ° C.) gave a residue which was then dissolved in about 500 ecm of ethyl acetate aqueous citric acid solution, then with 15 ecm of a 7% sodium bicarbonate solution and finally with 3 parts of sodium chloride solution. After drying over IMa ₂ SO. and evaporation, the residue obtained was the methyl ester of N-carbobenzoxyl dipeptide. This compound can be prepared according to one of the following Process can be converted into their open-chain or cyclic Dipepticj:

A. Preparation of an open-chain dipeptide

The methyl ester of N-carbobenzoxylic dipeptide prepared as above was saponified by the method of Wieland (Lieb.Ann. 1973 , 45) by dissolving the crude product in 80 ecm of dioxane and 5 ecm of 1N NaOH and then stirring the clear solution for 1 hour at room temperature . '

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_1D _ 2.445874

The volatile components were evaporated off under reduced pressure at 20 ° C., and the residue obtained was dissolved in 100 ecm of water and washed twice with 50 cc. Of ethyl acetate each time. The aqueous phase was acidified with 2N HCl to a pH value of 1 and then extracted four times with 100 ecm of ethyl acetate each time. After the usual drying over Na _? S0. and evaporation gave a residue which was catalytically hydrogenated in the presence of palladium on carbon.

B. H ^ r st e Settin g cyclic dipeptide

The above _y 3rd.Ute methyl ester of the N-carbobenzoxylic dipeptide was dissolved in 150 ecm of methanol and catalytically hydrogenated in the presence of palladium-on-animal charcoal. Usually 10 minutes are sufficient for complete conversion; however, the solution was kept under a stick of fatmosphere for 3 hours.

After filtering, evaporation of the clear filtrate gave a residue which was mainly composed of the M ^ thylester. open-chain Dipeptides; this could then be cyclized according to the method of f'itecki et al, D.Org.Chem., 22> ⁸⁶ ^ (ΐ96ο) by heating in about 200 ecm of a 96: 4 mixture of toluene and sec-butanol for 3 hours will. The cyclic dipeptide obtained by evaporation of the volatile components was crystallized in methanol.

(Cyclo) -Pr-o-Asn-, which is a new compound, shows the following physical data:

F, 200-202 ° C I / TcCp ⁰ CH ₂ O) * -C ';. 8 ^O C

NMR (DMSO): 1.78 ( ¹ III, m) J 2. ^ 0 (2H, m); 3.70-'1.1JO (»Ul, m) J

6.75 (IH, broad s); 7-28 (IH, broad s) j

7.80 (IH, s) S ppm.

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The compound can be represented by the following structural formula: O

(3S-Acetamido-1,4-dioxo-5C-2,5-pyrrolopiperazine or (Cyclo) -L-

Pro-L-Asn).

A D.iastereoxEomex-es of this lipeptide had the tolenden physical Characteristics:

F. »2i) 9-25O ° CJ Λί7ρ ° (Η ₂ 0) = ~ 6l, 7 ° C

NMR (PmQ) 'x 1.75 (W, m); 2.38 (3H, m); 3.65- ^ 0 (3H, m) j

7.30 (IH ₅ broad s) } 7.92 (lH, d, d = ¹ I cpa) 5 ypn.

According to the method of Fischer (cf. Ber., 22? ^ ⁵³ (1905)) the following symmetrical cyclic dipeptides were produced: (Cyclo) -Gly-Glv-, (Cyclo) -Ala-Ala-, (CyCIo) -VaI-VaI-,

(Cyclo) -Leu-Leu-, (Cyclo) -Phe-Ph3-.

The methyl esters of the chosen amino acids were ^{heated to about 110 D} C. for 3 hours, the reaction mixture was solidified and the product was purified by crystallization in methanol.

Of the various dligopeptides suitable according to the invention the cyclic dipeptides are preferred.

Wherever it was found to be the most interesting aroma effects obtained by using preparations that are a mixture of at least two of the above cyclic Dipeptiae comprises, the relative proportions of which can vary within a wide range.

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According to a preferred embodiment of the present invention is preferred as Purxn theobromine.

A particular object of the present invention is a flavor preparation, the active ingredient is a cyclic dipeptide (diketopiperazine) in combination with thuobromine.

The proportions of the preparations according to the invention which are necessary to achieve bines interesting flavoring effect can be used should, απ and / eiten limits can vary. So can ^ .B. Circumstances by 5-10 ppm based on the total weight of the flavored Material to which they are added already gives noticeable effects ^ These proportions, however, are preferable about 50-500 ppm. To achieve special effects you can higher ratios are used:

If the preparations according to the invention are used to create new aromatic preparations, these ratios can be up to about 19 % or even more, but preferably up to 1 ^ of the weight of the preparation. D ^ s ratio between the respective interests of each Aromatisierungsbestandteiles in the inventive preparations · ^"1 also could vary widely if the preparation consists of a mixture of two Peptides and theobromine, particularly expedient Gewichtoverhältnisse the respective shares are each ingredient between about. 1: 1: 1 and 1: 3: 5. For example, the following standard preparations were made by mixing the specified ingredients in the specified proportions:

50981S / 1328

2445674 Weight Parts 10 20th 1 00 ' 30th 30th 1 00

(Cyclo) -Phe-Phen- (Cyclo) -Phe-Val- " Theobromine

(Cyclo) -Phe-G3y- (CyCIo) -AIa-VaI-theobromine

Due to the presence of one; or several asymmetric carbon atoms in their molecule, the amino acids or polypeptides according to the invention can occur in the form of isomers with different configurations. For example, the designation "Ala-Phe ¹¹ or (" Cyclo) -Alci-Phe- "can never mean the following isomeric peptides:

ι D-Ala-L-Phe _{hziU #} (CyclcO-D-Ala-L-Phc- \

D-AIa-D-Phe (Cyclo) -D-Ala-D-Phe- · |

L-Ala-D-Phe (Cyclo) -L-Ala-D-Phe-

L-Ala-L-Phe ■ (Cyclo) -L-AIa-L -Phe-,

Due to the similarity of their organoleptic properties can each of these isomers by one of the other or. Mixtures of the same be replaced without the achieved Aror ^ a noticeable is affected.

The production of the differently configured isomies of the cyclic dipeptides is carried out according to the method given above (see reaction scheme). This is how, for example, the four are made. Isomers of (cyclo) -Ala-Phe- by coupling equimolecular amounts of the ^ j-carbobenzoxylic derivative of L-alanine and of the racamic Methyl ester of phenylalanine hydrochloride on the one hand and the N-carbohenzoxylic derivative of D-alanine and the race-

509815/132 8

mix methyl ester of phenylalanine hydrochloride on the other hand. So two pairs of diastereoisomers are obtained, which according to
Separation by column chromatography on silica gel yields the four compounds in their pure isomeric form.

The following table summarizes the different isomeric forms composed of two members of the above class of cyclic dip ^ ptides, namely (Cyclo) -Ala-Phen- and (CyLIo) -AIa-UaI-. Next to dan analytical data was derived from the nature of their manufacture used starting materials called.

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cycl.Dipep.tid Source material COOH <?: ■ · F. ^C D re Analysis ■ 'him et 55 N. found % c 6.51 12.84 Lit. ' • "NH ₉ - · page ( ⁰ O % c 12.81} 65.90 6.59 12.82. (D .Page PheOMe H ₂ O 66.05 6.42 12.84 65.90 6.53 12.87 (Cyclo) -L-Ala-L-Phe-. Z-L-AIa- PheOMe 266-267 '■ »31.5 ° 66.05 6.42 12.84 65.91 6.59 12.9? (Cyclo) -D-Ala-D-Phe- Z-D-AIa- PheOMe 266-268 -60.0 ° 66.05 6.42 12.84 65.97 8.28 16.38 (Cyclo) -D-Ala-L-Phe- Z-D-AIa- PheOMe 253-256 + 80.1 ° 66.05 6.42 16.47 56.20 8.30 16.54 (Cyclo) -L-Ala-D-Jrhe - Z-L-AIa- VaIOMe 253-255 -80.0 ° 56.49 8.24 16.47 Γ5Γ.31 8.26 16.32 (Cyclo) -L-AIa-L-VaI- Z-L-AIa- VaIOMe 263-265 -54.7 ° 56.49 8.24 16.47 55.63 8.20. 16.46 (Cyclo) -D-AIa-D-VaI- Z-D-AIa- VaIOMe 268-27O + 48.9 ° 56.49 8.24 16.47 56.01 (Cyclo) -L-AIa-D-VaI- Z-L-AIa- ■ VaxOMe 273-276 -2Cr ⁰ 56.49 8.24 (Cyclo) -D-AIa-L-VaI- Z-D-AIa- 272-275 + 38.6 °

Z = N-carbobenzoxylic radical

(1) W. Schöller, doctoral thesis, Univ. Berlin (1906)

(2) E. Fischer and H. Sensibler, Ann * Chern., O63_, 136 (1903)

in <cn

The following examples illustrate the present invention without limiting it.
Be is ρ ie Ie
A.

There was a Aromatisierungspräparat prepared by mixing 1-stiindiges ^e n f of the repaid in the specified oligopeptides and theobromine in 100 cc of commercial Kuhm.r? Ch with vigorous stirring.

To the solution obtained in this way, 0.08 ecm of a 10% alcoholic

one
Lisch? n solution (95% ethanol) / commercial cocoa flavor preparations without bitter taste (Firme'nich SA. Geneva, Switzerland, No. 51490 ") and 2 g of soluble cocoa powder with a neutral taste added.

The taste of the drink thus obtained was determined by comparison with gin em drink evaluated by dissolving 4 g of soluble Cocoa powder was made in 100 ecm milk.

The aroma experts agreed that the drink flavored with the above aroma preparation had a natural cocoa aroma, in particular with regard to its bitter and astringent character. In fact, its aroma was largely similar to that developed by a drink made with soluble cocoa alone.
B.

A second trial was to evaluate the im the following specified preparations in mineral water (type: Evian) by comparison with solutions obtained by dissolving 2 g of soluble Cocoa powder was made in 50 ecm of mineral water. It

509815/1328

the following ratios were used:

3 mg oligopeptide 6 mg theobromine 30 ecm mineral water.

The table below shows the various preparations that have been tried according to a relative rating scale, namely "strong" bitter "," bitter "and" light pleasei "classified.

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Ex. •Preparation evaluation • slightly bitter 1 1 rag (Cyclo) -Fhe-Phe- - '2 mg (Cyclo) -Phe-Val- strongly bitter 10 mg thebbromine bitter 1.5 mg (Cyclo) -Phe-Phe- strong-bitter 3 mg (CyCZo) -AT ^ -VaI- 3 10 ^ g Tiieobromine: ■. strongly bitter 3 mg (Cyclo) -Phe - Gly • "3 mg (Cyclo) -Ala-Val- 10 mg T-heobromine ·; bitter 5 3 mg (Cyclo) -Pro-Ala- 3 mg (Cyclo) -Gly-Gly- 10, g theobromine bitter 6th 3 mg (Cyclo) -Ala-Gly- 3 mg (Cyclo) -Leu-Leu- 10 mg theobromine. . · 7th 3 mg (Cyclo) -Phe-Pro- 3 mg (Cyclo) -Gly-Gly- 10 mg theobromine 3 mg (Cyclo) -Phe-Pro- J mg (Cyclo) -Leu-Leu- • 10 mg theobromine

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P ' 3 mg (Cyclo) -Leu-Gly-
3 mg (CVcIo) -Pro-Asp-
10 mg of i'heobromine oitter 9 3 mg (Cyclo) -Val-Gly-
3 mg vCyloJ'-Phe-Leu-
3 0 mg T ^ hcobror ^ ni " slightly bitter
I. 10 3 mg (Cyclo) -Ala-Pro-
3 mg (Cyclo) -Pne-Val-
10 mg theobromine c + .ark bitter 11
I. 5.5 mg ν Cyclo) -Phe-Val-
10 m '^ theobromine ■ · .- >. strongly bitter 12th 5.Γ mg (Cyclo) -Leu-Gly-
10 mg theobromine ; ■■ slightly bitter 13th 11 mg Val-Phe-
10 mg theobr-omin • slightly pleasei IH 3 mg (Cyclo) -Phe-Gly-
6 n _>d; Theobromine
'I. bitter 15th 3 mg (Cyclo) -Phe-Ala-
6 mg theobromine , very bitter

50981 5/1328

if. 3 mg (Cycloi-Phe-Leu- '
6 mg of tiicobromine "very bitter 17th • very bitter 18th 3 mg (Cyclo) -Phe-Val-
b mg 'Pbeobromine 19th slightly bitter 20th 3 mg (Cyclo) -? He-Pro-
6 mg Xheobrrmiri ' . strongly bitter 21 bitter 22nd 3 mg ίcyclo) -Phe-Phe-
6 mg theobromime> bitter . 23
* bitter 2k 3 mg (Cyclo) -Leu Leu-
6 rcg theobromine ι slightly bitter bitter i, mg (Cyclo) -Leu-VaI-
6 mg thecbrorain 3 mg (Cyclo) -Leu-Ala-
6 mg theobromir. 3 mg (Cyclo) -Leu-Pro-
6 mg theobromine ■ ' ? mg (Cyclo) -L-Val-L-Ala-
6 mg theobrominv

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25th ■ 3 mg (Cyclo) -L-Val-L-Gly-
6 mg theobromine leicb + bitter 26th 3 mg (CyCIo) -L-AIa-L-AIa-
6 mg theobromine . slightly bitter 27 3 mg (CyCIo) -L-AIa-L-Gj.y-
6 mg theobromine ■ slightly bitter 28 3 mg (Cyclo) -L-AIa-L -Pr o-
6 mg T; heobromin ' .lightly- · bitter 29 3 mg "(CyCIc) -LG-Iy-L-GIy-
£ mg Theobromir- * \. slightly bitter 30th 3 mg (nyclo) -L-Gly-L-Pro-
6 mg theobromine , - ;. slightly bitter 31 3 mg (CycloJ-L-Pro-L-Asn-
6 mg theobromine bitter. 32 3 mg (Cyclo) -L-Pro-L-Asp-
6 mg The ^ bromin? . ·. slightly bitter 33 3 mg (Cyclo) -D-Phe-Val-
6 mg tiheobromine ^: • very bitter

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31 3 mg (Cyclo) -Phe-D-Val-
6 mg theobromine irv strong ■ bitter 35 3 mg 'Cyclo) -D-Phe-D-Val-
6 mg theobromime ■ 'strongly bitter '36 3 'mg (Cyclo) -D-Val ~ Ala-
6 mg theobromine bitter 37
38 3 me (Cyclo) -Val-D-Ala-
6 mg iheobromim . bitter 39 3 rag (Cyclo) -D-Val-D-Ala-
6 mg theobroinine bitter 10 3 mg (CyCIo) -PT ¹ OD-ASn-
6 mg tjifjobromine bitter 3 mg (Cyclo) -Asn-Phe-
6 mg theobromine bitter

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Claims (10)

Patent appli c _w he 1, - Mixture, in particular flavoring agents, containing as active Constructs the connections A and G, u / obei the connection A is an amino acid cr an oligopeptide or a mixture of Is oligopeptides and compound B is a purine peptide. the Formula: 1 2 is, in which R and R each stand for a methyl radical or one of the substituents is a hydrogen atom and the other a Fiethyl ^ est. 2.- flavoring agent according to claim 1, characterized in that the Oligopeptide is a di-, tri-, tetra-, penta- cder hexapeptide. 3.- flavoring agent to ^fl nspruch 2, characterized in that ds ° dipeptide having a cyclic structure. 4, - flavoring agent according to claim i ', ^H ABy in that the mixture of oligopeptides comprises aur ziuei cyclic dipeptides. 5.- flavoring agent according to claim 1 to 4, characterized in that the purine derivative is theobramine. 6.- flavoring agent according to claim 3 and 5, characterized in that the cyclic dipeptide (cyclo) -Phe-Val-, (cyclo) -Phe-Leu- or (cyclo) -Phe-Ala-. 7.- flavoring agent according to claim 4 un ^ 5, characterized in that that the mixture of two cyclic dipeptides 509815/1328 SubsequentI a. (Cyclo) -Phe-Phe- (Cyclo) -Phe- '«/ al- b. (Cyclo) -Phen-Phe- (Cyclo) -Ala-Val- c. (Cyclo) -Phe-Gly- or (Cyclo-Phe-Phe) (Cyclo) -Ala-Val- d. (Cyclo) -Ala-Pro- (Cyclo) -Phe-Val- 8, - The use of the mixtures according to claims 1 to 7 as Flavorings in food, beverages, luxury foods, pet food, pharmaceuticals and tobacco products. 9.- embodiment according to claim 8, characterized in that the mixtures in cocoa, cocoa products or cocoa imitating Substitute substances used u / earth, especially in amounts of about 50-5000 ppm, based on the weight of the to be flavored Product. 10. 3-Acetamido-1,4-dioxo-2,5-pyrrolopiperazine. The patent attorney: 5 09815/1328